Supported biscyclopentadienyl metal complexes

ABSTRACT

Metal complexes corresponding to the formula: ##STR1## wherein: L independently each occurrence is a delocalized, π-bonded group that is bound to M, containing up to 50 nonhydrogen atoms; 
     M is a metal of Group 3, 4 or the Lanthanide series of the Periodic Table of the Elements; 
     Z is a covalently bound, divalent substituent of up to 50 non-hydrogen atoms having the formula, --(ER 2 ) m  --, wherein E independently each occurrence is carbon, silicon or germanium, R independently each occurrence is selected from the group consisting of C 1-20  hydrocarbyl, and C 1-20  hydrocarbyloxy, with the proviso that in at least one occurrence R is C 1-20  hydrocarbyloxy, and m is an integer from 1 to 3; 
     X&#39; is a neutral Lewis base ligand having up to 20 non-hydrogen atoms; 
     X&#34; independently each occurrence is a monovalent, anionic moiety selected from hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy, amide, siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, and aminohydrocarbyl having up to 20 non-hydrogen atoms, or two X&#34; groups together form a divalent hydrocarbadiyl or neutral hydrocarbon group; 
     n is a number from 0 to 3; and 
     p is an integer from 0 to 2.

This invention relates to metal complexes containing twocyclopentadienyl or substituted cyclopentadienyl moieties and toaddition polymerization catalysts formed there from that have improvedcatalytic performance, especially when supported on aluminum or siliconcontaining supports. More particularly such complexes are Group 3, 4, orLanthanide metal complexes containing one or more hydrocarboxysubstituted silane bridging groups. In addition, the present inventionrelates to the process for preparing supported derivatives of suchcomplexes and to a method of using such complexes in an additionpolymerization process for polymerizing addition polymerizable monomers.

In U.S. Pat. No. 4,892,851 there are disclosed biscyclopentadienyl Group4 metal complexes, especially complexes of zirconium or hafnium that areusefully employed with alumoxane activating cocatalysts for use inaddition polymerizations, especially the polymerization of aliphaticα-olefins. In a series of patents, W. Spaelick has disclosed certainring substituted stereorigid bisindenyl complexes and their use asolefin polymerization catalysts. The bridging group of such complexesgenerically includes silicon, germanium or tin containing divalentgroups containing hydride, halogen, C₁₋₁₀ alkyl, C₁₋₁₀ fluoroalkyl,C₆₋₁₀ aryl, C₆₋₁₀ fluoroaryl, C₁₋₁₀ alkoxy, C₂₋₁₀ alkenyl, C₇₋₄₀aralkyl, C₈₋₄₀ aralkenyl or C₇₋₄₀ alkylaryl groups or ring formingcombinations thereof. Such disclosure may be found in U.S. Pat. Nos.5,243,001, 5,145,819, 5,304,614, 5,350,817, among others. For theteachings contained therein, the foregoing United States patents andapplications are herein incorporated by reference.

It would be desirable if there were provided improved metal complexesthat are more readily adaptable to forming supported catalyst systems aswell as an improved addition polymerization process utilizing suchcatalyst systems.

SUMMARY OF THE INVENTION

As a result of investigations carried out by the present inventors therehave now been discovered new and improved Group 3, 4, or Lanthanidemetal complexes corresponding to the formula: ##STR2## or a dimer,solvated adduct, chelated derivative or mixture thereof, wherein:

L independently each occurrence is a delocalized, π-bonded group that isbound to M, containing up to 50 nonhydrogen atoms;

M is a metal of Group 3, 4 or the Lanthanide series of the PeriodicTable of the Elements;

Z is a covalently bound, divalent substituent of up to 50 non-hydrogenatoms having the formula, --(ER*₂)_(m) --, wherein E independently eachoccurrence is carbon, silicon or germanium, R* independently eachoccurrence is selected from the group consisting of C₁₋₂₀ hydrocarbyl,and C₁₋₂₀ hydrocarbyloxy, with the proviso that in at least oneoccurrence R* is C₁₋₂₀ hydrocarbyloxy, and m is an integer from 1 to 3;

X' is a neutral Lewis base ligand having up to 20 non-hydrogen atoms;

X" independently each occurrence is a monovalent, anionic moietyselected from hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy,amide, siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, andaminohydrocarbyl having up to 20 non-hydrogen atoms, or two X" groupstogether form a divalent hydrocarbadiyl or neutral hydrocarbon group;

n is a number from 0 to 3; and

p is an integer from 0 to 2.

There are also provided improved catalyst compositions comprising one ormore of the foregoing Group 3, 4 or Lanthanide metal complexes and oneor more activating cocatalysts.

In a further embodiment there is provided a supported catalyst systemcomprising one or more of the foregoing metal complexes, one or moreactivating cocatalysts, and an aluminum or silicon containing supportmaterial.

Finally there is provided an improved method for polymerization ofaddition polymerizable monomers using one or more of the above additionpolymerization catalysts or catalyst systems. Such additionpolymerization processes may be used to prepare polymers for use inmolding, film, sheet, extrusion foaming and other applications.

DETAILED DESCRIPTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1989. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups.

Suitable L groups for use herein include any neutral or anionicπ-electron containing moiety capable of forming a delocalized bond withthe Group 3, 4 or Lanthanide metal. Examples of such neutral groupsinclude arene moieties such as benzene, anthracene or naphthalene, aswell as substituted derivatives of such groups. Examples of anionicπ-electron containing moieties include allyl, pentadienyl,cyclopentadienyl, cyclohexadienyl, as well as substituted derivatives ofsuch groups.

By the term "derivative" when used to describe the above substituted,delocalized π-bonded groups is meant that each atom in the delocalizedπ-bonded group may independently be substituted with a radical selectedfrom the group consisting of hydrocarbyl radicals, halo-, alkoxy-,amino- or cyano-substituted hydrocarbyl radicals, andhydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements. Suitablesubstituents of the delocalized π-bonded groups contain from 1 to 20nonhydrogen atoms. Suitable hydrocarbon substituents include straightand branched alkyl radicals, cycloalkyl radicals, aryl radicals, andalkyl-substituted cycloalkyl or aryl radicals. In addition two or moresuch radicals may together form a fused ring system or a hydrogenatedfused ring system. Examples of the latter are indenyl-,tetrahydroindenyl-, fluorenyl-, and octahydrofluorenyl-groups, as wellas ring alkyl substituted derivatives thereof. Examples of suitablehydrocarbyl-substituted organometalloid radicals include trimethylsilyl,triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl,and trimethylgermyl.

Preferred L groups are anionic L groups, including, cyclopentadienyl,indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl,hexahydroanthracenyl, decahydroanthracenyl groups, and C₁₋₁₀hydrocarbyl-substituted derivatives thereof. Most preferred anionic Lgroups are pentamethylcyclopentadienyl, 2-methylindenyl,3-methylindenyl, 2,3-dimethylindenyl, 2-methyl-4-phenylindenyl, and2-methyl-4-naphthylindenyl.

Examples of highly preferred complexes according to the presentinvention correspond to the formula: ##STR3## wherein:

M is titanium, zirconium or hafnium, in the +2, +3 or +4 formaloxidation state;

E independently each occurrence is carbon or silicon;

R* independently each occurrence is selected from the group consistingof C₁₋₆ hydrocarbyl, and C₁₋₆ hydrocarbyloxy, with the proviso that inat least one occurrence R* is C₁₋₆ hydrocarbyloxy;

m is 1 or 2;

R' independently in each occurrence is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R' having up to 20 non-hydrogen atoms each,or adjacent R' groups together form a divalent derivative that is ahydrocarbadiyl, siladiyl or germadiyl group;

X' is a conjugated diene having from 4 to 30 non-hydrogen atoms, whichforms a π-complex with M when M is in the +2 formal oxidation state,whereupon n is 1 and p is 0;

X" each occurrence is an anionic ligand group that is covalently bondedto M when M is in the +3 or +4 formal oxidation state, whereupon n is 0and p is 1 or 2, and optionally two X" groups together for a divalentanionic ligand group.

Preferably, R' independently in each occurrence is selected from thegroup consisting of hydrogen, methyl, ethyl, and all isomers of propyl,butyl, pentyl and hexyl, as well as cyclopentyl, cyclohexyl, norbornyl,phenyl, naphthyl, benzyl, and trimethyl silyl; or adjacent R' groups arelinked together thereby forming a fused ring system such as an indenyl,2-methylindenyl, 3-methylindenyl, 2,3-dimethylindenyl,2-methyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, tetrahydroindenyl,fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group.

Preferred L groups include cyclopentadienyl,tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,tetrahydrofluorenyl, octahydrofluorenyl, or one of the foregoing groupsfurther substituted with one or more methyl, ethyl, propyl, butyl,pentyl, hexyl, (including branched and cyclic isomers), norbornyl,benzyl, or phenyl groups.

Examples of suitable X' moieties include: η⁴-1,4-diphenyl-1,3-butadiene; η⁴ -1,3-pentadiene; η⁴-1-phenyl-1,3-pentadiene; η⁴ -1,4-dibenzyl-1,3-butadiene; η⁴-2,4-hexadiene; η⁴ -3-methyl-1,3-pentadiene; η⁴-1,4-ditolyl-1,3-butadiene; and η⁴-1,4-bis(trimethylsilyl)-1,3-butadiene. Of the foregoing,1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and 2,4 hexadieneare preferred.

Examples of suitable X" moieties include hydride, chloride, methyl,benzyl, phenyl, tolyl, t-butyl, methoxide, and trimethylsilyl or two X"groups together are 1,4-butanediyl, s-cis(1,3-butadiene), ors-cis(2,3-dimethyl-1,3-butadiene).

Most preferred Z groups are those wherein E is silicon, m is 1, and R*in at least one occurrence is methoxide, ethoxide, propoxide orbutoxide.

In the most preferred embodiment --Z-- is ethoxymethyl-silanediyl,isopropoxymethylsilanediyl 2-butoxymethylsilanediyl, diethoxysilanediyl,diisopropoxysilanediyl, or di(2-butoxy)silanediyl.

Illustrative derivatives of Group 3, 4 or Lanthanide metals that may beemployed in the practice of the present invention include:

ethoxymethylsilanediyl complexes:

ethoxymethylsilanebis(cyclopentadienyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,3-pentadiene,

ethoxymethylsilanebis(cyclopentadienyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(cyclopentadienyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (IV)dimethyl,

ethoxymethylsilane(cyclopentadienyl)(fluorenyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis (pentamethylcyclopentadienyl)zirconium (IV)dibenzyl,

ethoxymethylsilanebis(2-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(2-methylindenyl)zirconium (II) 1,3-pentadiene,

ethoxymethylsilanebis(2-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(2-methylindenyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis(2-methylindenyl)zirconium (IV) dibenzyl,

ethoxymethylsilanebis(3-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(3-methylindenyl)zirconium (II) 1,3-pentadiene,

ethoxymethylsilanebis(3-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(3-methylindenyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis(3-methylindenyl)zirconium (IV) dibenzyl,

ethoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II) 1,3-pentadiene,

ethoxymethylsilanebis(2,3-dimethylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dibenzyl,

ethoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,3-pentadiene,

ethoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV) dimethyl,

(ethoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV) dibenzyl,

ethoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

ethoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II) 1,3-pentadiene,

ethoxymethylsilanebis(tetrahydrofluorenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

ethoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dimethyl,

ethoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dibenzyl,

isopropoxymethylsilanediyl complexes:

isopropoxymethylsilanebis(cyclopentadienyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,3-pentadiene,

isopropoxymethylsilanebis(cyclopentadienyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

isopropoxymethylsilanebis(cyclopentadienyl)zirconium (IV) dimethyl,

isopropoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (IV)dimethyl,

isopropoxymethylsilane(cyclopentadienyl)(fluorenyl)zirconium (IV)dimethyl,

isopropoxymethylsilanebis (pentamethylcyclopentadienyl)zirconium (IV)dibenzyl,

isopropoxymethylsilanebis(2-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(2-methylindenyl)zirconium (II) 1,3-pentadiene,

isopropoxymethylsilanebis(2-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

isopropoxymethylsilanebis(2-methylindenyl)zirconium (IV) dimethyl,

isopropoxymethylsilanebis(2-methylindenyl)zirconium (IV) dibenzyl,

isopropoxymethylsilanebis(3-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(3-methylindenyl)zirconium (II) 1,3-pentadiene,

isopropoxymethylsilanebis(3-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

isopropoxymethylsilanebis(3-methylindenyl)zirconium (IV) dimethyl,

isopropoxymethylsilanebis(3-methylindenyl)zirconium (IV) dibenzyl,

isopropoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II)1,3-pentadiene,

isopropoxymethylsilanebis(2,3-dimethylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

isopropoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dimethyl,

isopropoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dibenzyl,

isopropoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,3-pentadiene,

isopropoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

sopropoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV)dimethyl,

(isopropoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV)dibenzyl,

isopropoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

isopropoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II)1,3-pentadiene,

isopropoxymethylsilanebis(tetrahydrofluorenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

isopropoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dimethyl,

isopropoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dibenzyl,

2-butoxymethylsilanediyl complexes:

2-butoxymethylsilanebis(cyclopentadienyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (II)1,3-pentadiene,

2-butoxymethylsilanebis(cyclopentadienyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(cyclopentadienyl)zirconium (IV) dimethyl,

2-butoxymethylsilanebis(pentamethylcyclopentadienyl)zirconium (IV)dimethyl,

2-butoxymethylsilane(cyclopentadienyl)(fluorenyl)zirconium (IV)dimethyl,

2-butoxymethylsilanebis (pentamethylcyclopentadienyl)zirconium (IV)dibenzyl,

2-butoxymethylsilanebis(2-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(2-methylindenyl)zirconium (II) 1,3-pentadiene,

2-butoxymethylsilanebis(2-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(2-methylindenyl)zirconium (IV) dimethyl,

2-butoxymethylsilanebis(2-methylindenyl)zirconium (IV) dibenzyl,

2-butoxymethylsilanebis(3-methylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(3-methylindenyl)zirconium (II) 1,3-pentadiene,

2-butoxymethylsilanebis(3-methylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(3-methylindenyl)zirconium (IV) dimethyl,

2-butoxymethylsilanebis(3-methylindenyl)zirconium (IV) dibenzyl,

2-butoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(2,3-dimethylindenyl)zirconium (II)1,3-pentadiene,

2-butoxymethylsilanebis(2,3-dimethylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dimethyl,

2-butoxymethylsilanebis(2,3-dimethylindenyl)zirconium (IV) dibenzyl,

2-butoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (II)1,3-pentadiene,

2-butoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV)dimethyl,

(2-butoxymethylsilanebis(2-methyl-4-phenylindenyl)zirconium (IV)dibenzyl,

2-butoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

2-butoxymethylsilanebis(tetrahydrofluorenyl)zirconium (II)1,3-pentadiene,

2-butoxymethylsilanebis(tetrahydrofluorenyl)zirconium (III)2-(N,N-dimethylamino)benzyl,

2-butoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dimethyl,

and

2-butoxymethylsilanebis(tetrahydrofluorenyl)zirconium (IV) dibenzyl.

Other metal complexes, especially compounds containing other Group 3, 4or Lanthanide metals will, of course, be apparent to those skilled inthe art.

The complexes are rendered catalytically active by combination with anactivating cocatalyst or by use of an activating technique. Suitableactivating cocatalysts for use herein include polymeric or oligomericalumoxanes, especially methylalumoxane, triisobutyl aluminum- modifiedmethylalumoxane, or diisobutylalumoxane; strong Lewis acids, such asC₁₋₃₀ hydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron-compounds andhalogenated derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, especiallytris(pentafluorophenyl)borane; and nonpolymeric, inert, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions). A suitable activating techniqueis bulk electrolysis (explained in more detail hereinafter).Combinations of the foregoing activating cocatalysts and techniques mayalso be employed if desired. The foregoing activating cocatalysts andactivating techniques have been previously taught with respect todifferent metal complexes in the following references: EP-A-277,003,U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, EP-A-468,651(equivalent to U.S. Ser. No. 07/547,718 now abandoned), EP-A-520,732(equivalent to U.S. Ser. No. 07/876,268 now U.S. Pat. No. 5,721,185),and WO93/23412(equivalent to U.S. Ser. Nos. 07/884,966 filed May 1, 1992now U.S. Pat. No. 5,350,723), the teachings of which are herebyincorporated by reference.

Suitable nonpolymeric, inert, compatible, noncoordinating, ion formingcompounds useful as cocatalysts in one embodiment of the presentinvention comprise a cation which is a Bronsted acid capable of donatinga proton, and a compatible, noncoordinating, anion, A⁻. Preferred anionsare those containing a single coordination complex comprising acharge-bearing metal or metalloid core which anion is capable ofbalancing the charge of the active catalyst species (the metal cation)which is formed when the two components are combined. Also, said anioncan be displaced by olefinic, diolefinic and acetylenically unsaturatedcompounds or other neutral Lewis bases such as ethers or nitrites.Suitable metals include, but are not limited to, aluminum, gold andplatinum. Suitable metalloids include, but are not limited to, boron,phosphorus, and silicon. Compounds containing anions which comprisecoordination complexes containing a single metal or metalloid atom arewell known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:

    (L*--H).sup.+.sub.D A.sup.d-

wherein:

L* is a neutral Lewis base;

(L*--H)⁺ is a Bronsted acid;

A^(d-) is a noncoordinating, compatible anion having a charge of d-, and

d is an integer from 1 to 3.

More preferably d is one, that is, A^(d-) is A⁻.

Highly preferably, A⁻ corresponds to the formula:

     BQ.sub.4 !.sup.-

wherein:

B is boron in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonswith the proviso that in not more than one occurrence is Q halide.

In a more highly preferred embodiment, Q is a fluorinated C₁₋₂₀hydrocarbyl group, most preferably, a fluorinated aryl group,especially, pentafluorophenyl.

Illustrative, but not limiting, examples of ion forming compoundscomprising proton donatable cations which may be used as activatingcocatalysts in the preparation of the catalysts of this invention aretri-substituted ammonium salts such as:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl(2,4,6-trimethylanilinium) tetraphenylborate,

trimethylammonium tetrakis-(penta-fluorophenyl) borate,

triethylammonium tetrakis-(pentafluorophenyl) borate,

tripropylammonium tetrakis(pentafluorophenyl) borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,tri(sec-butyl)ammonium

tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium

tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium

tetrakis(pentafluoro-phenyl) borate,N,N-dimethyl(2,4,6-trimethylanilinium) tetrakis-(pentafluorophenyl)borate,

trimethylammonium tetrakis(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, and

N,N-dimethyl--(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl) borate.

Dialkyl ammonium salts such as: di--(i-propyl)ammoniumtetrakis(pentafluorophenyl) borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl) borate.

Tri-substituted phosphonium salts such as: triphenylphosphoniumtetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphoniumtetrakis(penta-fluorophenyl) borate, andtri(2,6-dimethylphenyl)-phosphonium tetrakis(penta-fluorophenyl) borate.

Preferred are N,N-dimethylanilinium tetrakis(pentafluorophenyl)borateand tributylammonium tetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

    (Ox.sup.e+).sub.d (A.sup.d-).sub.e

wherein:

Ox^(e-) is a cationic oxidizing agent having charge e+;

e is an integer from 1 to 3; and

A^(d-), and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d-) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion or silylium ion and anoncoordinating, compatible anion represented by the formula:

    ©.sup.30 A.sup.-

wherein:

©⁺ is a C₁₋₂₀ carbenium ion or a silylium ion of up to 20 noncarbonatoms; and

A⁻ is as previously defined.

A preferred carbenium ion is the trityl cation, that istriphenylcarbenium, a preferred silylium ion is triphenylsilylium.

The foregoing activating technique and ion forming cocatalysts are alsopreferably used in combination with a tri(hydrocarbyl)aluminum compoundhaving from 1 to 4 carbons in each hydrocarbyl group, an oligomeric orpolymeric alumoxane compound, or a mixture of a tri(hydrocarbyl)aluminumcompound having from 1 to 4 carbons in each hydrocarbyl group and apolymeric or oligomeric alumoxane.

An especially preferred activating cocatalyst comprises the combinationof a trialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and an ammonium salt of tetrakis(pentafluorophenyl)borate, in amolar ratio from 0.1:1 to 1:0.1, optionally up to 1000 mole percent ofan alkylalumoxane with respect to M, is also present.

The activating technique of bulk electrolysis involves theelectrochemical oxidation of the metal complex under electrolysisconditions in the presence of a supporting electrolyte comprising anoncoordinating, inert anion. In the technique, solvents, supportingelectrolytes and electrolytic potentials for the electrolysis are usedsuch that electrolysis byproducts that would render the metal complexcatalytically inactive are not substantially formed during the reaction.More particularly, suitable solvents are materials that are: liquidsunder the conditions of the electrolysis (generally temperatures from 0°to 100° C.), capable of dissolving the supporting electrolyte, andinert. "Inert solvents" are those that are not reduced or oxidized underthe reaction conditions employed for the electrolysis. It is generallypossible in view of the desired electrolysis reaction to choose asolvent and a supporting electrolyte that are unaffected by theelectrical potential used for the desired electrolysis. Preferredsolvents include difluorobenzene (all isomers), DME, and mixturesthereof.

The electrolysis may be conducted in a standard electrolytic cellcontaining an anode and cathode (also referred to as the workingelectrode and counter electrode respectively). Suitably materials ofconstruction for the cell are glass, plastic, ceramic and glass coatedmetal. The electrodes are prepared from inert conductive materials, bywhich are meant conductive materials that are unaffected by the reactionmixture or reaction conditions. Platinum or palladium are preferredinert conductive materials. Normally, an ion permeable membrane such asa fine glass frit separates the cell into separate compartments, theworking electrode compartment and counter electrode compartment. Theworking electrode is immersed in a reaction medium comprising the metalcomplex to be activated, solvent, supporting electrolyte, and any othermaterials desired for moderating the electrolysis or stabilizing theresulting complex. The counter electrode is immersed in a mixture of thesolvent and supporting electrolyte. The desired voltage may bedetermined by theoretical calculations or experimentally by sweeping thecell using a reference electrode such as a silver electrode immersed inthe cell electrolyte. The background cell current, the current draw inthe absence of the desired electrolysis, is also determined. Theelectrolysis is completed when the current drops from the desired levelto the background level. In this manner, complete conversion of theinitial metal complex can be easily detected.

Suitable supporting electrolytes are salts comprising a cation and aninert, compatible, noncoordinating anion, A⁻. Preferred supportingelectrolytes are salts corresponding to the formula: wherein:

G⁺ is a cation which is nonreactive towards the starting and resultingcomplex, and

A⁻ is a noncoordinating, compatible anion.

Examples of cations, G⁺, include tetrahydrocarbyl substituted ammoniumor phosphonium cations having up to 40 nonhydrogen atoms. A preferredcation is the tetra-n-butylammonium cation.

During activation of the complexes of the present invention by bulkelectrolysis the cation of the supporting electrolyte passes to thecounter electrode and A⁻ migrates to the working electrode to become theanion of the resulting oxidized product. Either the solvent or thecation of the supporting electrolyte is reduced at the counter electrodein equal molar quantity with the amount of oxidized metal complex formedat the working electrode.

Preferred supporting electrolytes are tetrahydrocarbylammonium salts oftetrakis(perfluoroaryl) berates having from 1 to 10 carbons in eachhydrocarbyl group, especially tetra-n-butylammoniumtetrakis(pentafluorophenyl) borate.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:10 to 1:2.

In general, the catalysts can be prepared by combining the twocomponents in a suitable solvent at a temperature within the range fromabout ⁻ 100° C. to about 300° C. The catalyst may be separately preparedprior to use by combining the respective components or prepared in situby combination in the presence of the monomers to be polymerized. It ispreferred to form the catalyst in situ due to the exceptionally highcatalytic effectiveness of catalysts prepared in this manner. Thecatalysts' components are sensitive to both moisture and oxygen andshould be handled and transferred in an inert atmosphere.

As previously mentioned the present metal complexes are highly desirablefor use in preparing supported catalysts. The presence of the alkoxyfunctionality in the bridging group has been discovered to beparticularly beneficial in allowing the complexes to chemically bind toaluminum or silicon atoms of the matrix or hydroxyl, silane orchlorosilane functionality of the substrate materials. Especially suitedsubstrates include alumina or silica. Suitable supported catalystsystems are readily prepared by contacting the present metal complexeswith the substrate optionally while subjecting to heating and/or reducedpressures. A Lewis base, especially a trialkylamine can be present toassist in the reaction between the support and the siloxanefunctionality of the metal complexes.

Preferred supports for use in the present invention include highlyporous silicas, aluminas, aluminosilicates, and mixtures thereof. Themost preferred support material is silica. The support material may bein granular, agglomerated, pelletized, or any other physical form.Suitable materials include, but are not limited to, silicas availablefrom Grace Davison (division of W. R. Grace & Co.) under thedesignations SD 3216.30, Davison Syloid 245, Davison 948 and Davison952, and from Degussa AG under the designation Aerosil 812; and aluminasavailable from Akzo Chemicals Inc. under the designation Ketzen Grade B.

Supports suitable for the present invention preferably have a surfacearea as determined by nitrogen porosimetry using the B.E.T. method from10 to about 1000 m² /g, and preferably from about 100 to 600 m² /g. Thepore volume of the support, as determined by nitrogen adsorption,advantageously is between 0.1 and 3 cm³ /g, preferably from about 0.2 to2 cm³ /g. The average particle size is not critical, but typically isfrom 0.5 to 500 μm, preferably from 1 to 100 μm.

Both silica and alumina are known to inherently possess small quantitiesof hydroxyl functionality attached to the crystal structure. When usedas a support herein, these materials are preferably subjected to a heattreatment and/or chemical treatment to reduce the hydroxyl contentthereof. Typical heat treatments are carried out at a temperature from30° to 1000° C. for a duration of 10 minutes to 50 hours in an inertatmosphere or under reduced pressure. Typical chemical treatmentsinclude contacting with Lewis acid alkylating agents such astrihydrocarbyl aluminum compounds, trihydrocarbylchloro-silanecompounds, trihydrocarbylalkoxysilane compounds or similar agents.Preferred silica or alumina materials for use herein have a surfacehydroxyl content that is less than 0.8 mmol hydroxyl groups per gram ofsolid support, more preferably less than 0.5 mmol per gram. The hydroxylcontent may be determined by adding an excess of dialkyl magnesium to aslurry of the solid support and determining the amount of dialkylmagnesium remaining in solution via known techniques. This method isbased on the reaction:

    S-OH+Mg(Alk).sub.2 →S-OMg(Alk)+(Alk)H,

wherein S is the solid support, and Alk is a C₁₋₄ alkyl group.

The support may be unfunctionalized (excepting for hydroxyl groups aspreviously disclosed) or functionalized by treating with a silane orchlorosilane functionalizing agent to attach thereto pendant silane--(Si--R)═, or chlorosilane --(Si--Cl)═ functionality, wherein R is aC₁₋₁₀ hydrocarbyl group. Suitable functionalizing agents are compoundsthat react with surface hydroxyl groups of the support or react with thesilicon or aluminum of the matrix. Examples of suitable functionalizingagents include phenylsilane, diphenylsilane, methylphenylsilane,dimethylsilane, diethylsilane, dichlorosilane anddichlorodimethylsilane. Techniques for forming such functionalizedsilica or alumina compounds were previously disclosed in U.S. Pat. Nos.3,687,920 and 3,879,368, the teachings of which are herein incorporatedby reference.

The support may also be treated with an aluminum component selected froman alumoxane or an aluminum compound of the formula AlR¹ _(x),R² _(y),wherein R1 independently each occurrence is hydride or R, R² is hydride,R or OR, x' is 2 or 3, y' is 0 or 1 and the sum of x' and y' is 3.Examples of suitable R¹ and R² groups include methyl, methoxy, ethyl,ethoxy, propyl (all isomers), propoxy (all isomers), butyl (allisomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy.Preferably, the aluminum component is selected from the group consistingof aluminoxanes and tri(C₁₋₄ hydrocarbyl)aluminum compounds. Mostpreferred aluminum components are aluminoxanes, trimethyl aluminum,triethyl aluminum, tri-isobutyl aluminum, and mixtures thereof.

Alumoxanes (also referred to as aluminoxanes) are oligomeric orpolymeric aluminum oxy compounds containing chains of alternatingaluminum and oxygen atoms, whereby the aluminum carries a substituent,preferably an alkyl group. The structure of alumoxane is believed to berepresented by the following general formulae (--Al(R)--O)_(m'), for acyclic alumoxane, and R₂ Al--O(--Al(R)--O)_(m),--AlR₂, for a linearcompound, wherein R is as previously defined, and m' is an integerranging from 1 to about 50, preferably at least about 4. Alumoxanes aretypically the reaction products of water and an aluminum alkyl, which inaddition to an alkyl group may contain halide or alkoxide groups.Reacting several different aluminum alkyl compounds, such as for exampletrimethyl aluminum and tri-isobutyl aluminum, with water yieldsso-called modified or mixed alumoxanes. Preferred alumoxanes aremethylalumoxane and methylalumoxane modified with minor amounts of C₂₋₄alkyl groups, especially isobutyl. Alumoxanes generally contain minor tosubstantial amounts of starting aluminum alkyl compound.

Particular techniques for the preparation of alumoxane type compounds bycontacting an aluminum alkyl compound with an inorganic salt containingwater of crystallization are disclosed in U.S. Pat. No. 4,542,119. In aparticular preferred embodiment an aluminum alkyl compound is contactedwith a regeneratable water-containing substance such as hydratedalumina, silica or other substance. This is disclosed in EP-A-338,044.Thus the alumoxane may be incorporated into the support by reaction of ahydrated alumina or silica material, which has optionally beenfunctionalized with silane, siloxane, hydrocarbyloxysilane, orchlorosilane groups, with a tri(C₁₋₁₀ alkyl) aluminum compound accordingto known techniques. For the teachings contained therein the foregoingpatents and publications, or there corresponding equivalent UnitedStates applications, are hereby incorporated by reference.

The treatment of the support material in order to also include optionalalumoxane or trialkylaluminum loadings involves contacting the samebefore, after or simultaneously with addition of the complex oractivated catalyst hereunder with the alumoxane or trialkylaluminumcompound, especially triethylaluminum or triisobutylaluminum. Optionallythe mixture can also be heated under an inert atmosphere for a periodand at a temperature sufficient to fix the alumoxane, trialkylaluminumcompound, complex or catalyst system to the support. Optionally, thetreated support component containing alumoxane or the trialkylaluminumcompound may be subjected to one or more wash steps to remove alumoxaneor trialkylaluminum not fixed to the support.

Besides contacting the support with alumoxane the alumoxane may begenerated in situ by contacting an unhydrolyzed silica or alumina or amoistened silica or alumina with a trialkyl aluminum compound optionallyin the presence of an inert diluent. Such a process is well known in theart, having been disclosed in EP-A-250,600, U.S. Pat. No. 4,912,075, andU.S. Pat. No. 5,008,228, the teachings of which, or of the correspondingU.S. application, are hereby incorporated by reference. Suitablealiphatic hydrocarbon diluents include pentane, isopentane, hexane,heptane, octane, isooctane, nonane, isononane, decane, cyclohexane,methylcyclohexane and combinations of two or more of such diluents.Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene, andother alkyl or halogen substituted aromatic compounds. Most preferably,the diluent is an aromatic hydrocarbon, especially toluene. Afterpreparation in the foregoing manner the residual hydroxyl contentthereof is desirably reduced to a level less than 1.0 meq of OH per gramof support, by any of the previously disclosed techniques.

The catalysts, whether or not supported in any of the foregoing methods,may be used to polymerize ethylenically and/or acetylenicallyunsaturated monomers having from 2 to 100,000 carbon atoms either aloneor in combination. Preferred monomers include the C₂₋₂₀ α-olefinsespecially ethylene, propylene, isobutylene, 1-butene, 1-pentene,1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene,long chain macromolecular α-olefins, and mixtures thereof. Otherpreferred monomers include styrene, C₁₋₄ alkyl substituted styrene,tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, such as temperatures from 0°-250° C. andpressures from atmospheric to 1000 atmospheres (0.1 to 100 MPa).Suspension, solution, slurry, gas phase or other process conditions maybe employed if desired. The support, if present, is preferably employedin an amount to provide a weight ratio of catalyst (based onmetal):support from 1:100,000 to 1:10, more preferably from 1:50,000 to1:20, and most preferably from 1:10,000 to 1:30. Suitable gas phasereactions may utilize condensation of the monomer or monomers employedin the reaction, or of an inert diluent to remove heat from the reactor.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹² :1 to 10⁻¹ :1,more preferably from 10⁻¹² :1 to 10⁻⁵ :1.

Suitable solvents for polymerization via a solution process arenoncoordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons such as isobutane, butane, pentane, hexane,heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbonssuch as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbonssuch as perfluorinated C₄₋₁₀ alkanes, and aromatic and alkyl-substitutedaromatic compounds such as benzene, toluene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,1,4-hexadiene, 1,7-octadiene, 1-octene, 1-decene, styrene,divinylbenzene, ethylidenenorbornene, allylbenzene, vinyltoluene(including all isomers alone or in admixture), 4-vinylcyclohexene, andvinylcyclohexane. Mixtures of the foregoing are also suitable.

The catalysts may also be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame or in separate reactors connected in series or in parallel toprepare polymer blends having desirable properties. An example of such aprocess is disclosed in WO 94/00500, equivalent to U.S. Ser. No.07/904,770, now abandoned, as well as U.S. Ser. No. 08/10958, nowabandoned, filed Jan. 29, 1993, the teachings or which are herebyincorporated by reference herein.

One such polymerization process comprises: contacting, optionally in asolvent, one or more α-olefins with a catalyst according to the presentinvention, in one or more continuous stirred tank or tubular reactors,or in the absence of solvent, optionally in a fluidized bed gas phasereactor, connected in series or parallel, and recovering the resultingpolymer. Condensed monomer or solvent may be added to the gas phasereactor as is well known in the art.

In another process an ethylene/α-olefin interpolymer composition isprepared by:

(A) contacting ethylene and at least one other α-olefin underpolymerization conditions in the presence of a catalyst composition ofthe present invention in at least one reactor to produce a firstinterpolymer or optionally a solution of a first interpolymer,

(B) contacting ethylene and at least one other α-olefin underpolymerization conditions and at a higher polymerization reactiontemperature than used in step (A) in the presence of a heterogeneousZiegler catalyst in at least one other reactor to produce a secondinterpolymer optionally in solution, and

(C) combining the first interpolymer and second interpolymer to form anethylene/α-olefin interpolymer blend composition, and

(D) recovering the ethylene/α-olefin interpolymer blend composition.

Preferably the heterogeneous Ziegler catalyst comprises:

(i) a solid support component comprising magnesium halide, silica,modified silica, alumina, aluminum phosphate, or a mixture thereof, and

(ii) a transition metal component represented by the formula:

    TrX".sub.u (OR'").sub.v-u, TrX".sub.u R'".sub.v-u, VOX".sub.3 or VO(OR'").sub.3.

wherein:

Tr is a Group 4, 5, or 6 metal,

u is a number from 0 to 6 that is less than or equal to v,

v is the formal oxidation number of Tr,

X" is halogen, and

R'" independently each occurrence is a hydrocarbyl group having from 1to 20 carbon atoms.

These polymerizations are generally carried out under solutionconditions to facilitate the intimate mixing of the twopolymer-containing streams. The foregoing technique allows for thepreparation of ethylene/α-olefin interpolymer compositions having abroad range of molecular weight distribution and compositiondistribution. Preferably, the heterogeneous catalyst is also chosen fromthose catalysts which are capable of efficiently producing the polymersunder high temperature, especially, temperatures greater than or equalto 180° C. under solution process conditions.

In a still further embodiment, there is provided a process for preparingan ethylene/α-olefin interpolymer composition, comprising:

(A) polymerizing ethylene and at least one other α-olefin in a solutionprocess under suitable solution polymerization temperatures andpressures in at least one reactor containing a catalyst composition ofthe present invention to produce a first interpolymer solution,

(B) passing the interpolymer solution of (A) into at least one otherreactor containing a heterogeneous Ziegler catalyst, in the presence ofethylene and optionally one other α-olefin under solution polymerizationconditions to form a solution comprising the ethylene/α-olefininterpolymer composition, and

(C) recovering the ethylene/α-olefin interpolymer composition.

Preferably the heterogeneous Ziegler catalyst comprises:

(i) a solid support component comprising a magnesium halide or silica,and

(ii) a transition metal component represented by the formula:

    TrX".sub.u (OR'").sub.v-u, TrX,.sub.u R'".sub.v-u, VOX".sub.3 or VO(OR'").sub.3.

wherein:

Tr, X", u, v, and R'" are as previously defined.

The foregoing technique also allows for the preparation ofethylene/α-olefin interpolymer compositions having a broad range ofmolecular weight distributions and composition distributions.Particularly desirable α-olefins for use in the foregoing processes areC₄₋₈ α-olefins, most desirably 1-octene.

The skilled artisan will appreciate that the invention disclosed hereinmay be practiced in the absence of any component which has not beenspecifically disclosed. The following examples are provided as furtherillustration thereof and are not to be construed as limiting. Unlessstated to the contrary all parts and percentages are expressed on aweight basis.

EXAMPLES

Materials and Methods.

Unless otherwise stated, all chemical manipulations were performed undernitrogen in either an inert atmosphere glove box or on a nitrogen/vacuumdouble manifold using standard Schelenk techniques. Zirconiumtetrachloride, dichlorodimethylsilane, triethylamine, and 2-propanol areused as received from Aldrich Chemicals Inc.

Example 1isopropoxymethylsilanebis(tetramethylcyclopentadienyl)zirconiumdichloride

Preparation of (isopropoxy)methyldichlorosilane

To 45 mL (0.38 moles) of trichloromethylsilane in 1.5 L of anhydrousether cooled at 0° C. in an ice bath was added 51.5 mL (0.38 moles) oftriethylamine followed by dropwise addition of 29.5 mL (0.38 moles) of2-propanol. After stirring for 4 hours, the precipitated white solid(triethylamine hydrochloride) was removed by filtration and washed with2×100 mL portions of ether. The ether filtrate and washings were thencombined and the solvent removed under reduced pressure leaving thedesired product.

Preparation of isopropoxymethylsilanebis(tetramethylcyclopentadiene)

To 7.9 g (0.05 moles) of MeSi(OiPr)Cl₂ dissolved in 500 mL oftetrahydrofuran at 0° C. is added 16.0 g (0.10 moles) of potassiumtetramethylcyclopentadienide over a 1 hour period. The mixture isbrought to reflux and then stirred at room temperature for 4 hour. Theslurry is filtered, and washed with tetrahydrofuran and the solventremoved under vacuum to yield the desired product.

Preparation of Dilithiumisopropoxymethylsilanebis(tetramethylcyclopentadienide)!

To 2.0 g (5.8 mmoles) ofisopropoxymethylsilanebis(tetramethylcyclopentadiene in 50 mL ofdiethylether at 0° C. is added dropwise 2.3 mL of n-BuLi (2.5M inhexanes) over a 1 hour period. The mixture is stirred at roomtemperature for 6 hours. The solvent is removed under vacuum and theresidue washed with hexane to yield the desired product.

Preparation ofisopropoxymethylsilanebis(tetramethylcyclopentadienyl)zirconiumdichloride

To 2.0 g (5.6 mmol) of dilithiumisopropoxymethylsilanebis(tetramethylcyclopentadienyl) in 50 mL of THFis slowly added 1.3 g (5.6 mmol) of ZrCl₄ over a 30 minute period. Afterfurther stirring for three hours the solvent is removed under reducedpressure and the remaining solid recrystallized from n-pentane at -37°C. to yield the desired product.

Polymerization

A two-liter Parr reactor was charged with 740 g of Isopar-E™ mixedalkanes solvent (available from Exxon Chemicals Inc.) and 118 g of1-octene comonomer. Hydrogen is added as a molecular weight controlagent by differential pressure expansion from a 75 mL addition tank at25 psi (2070 kPa). The reactor is heated to the polymerizationtemperature of 140° C. and saturated with ethylene at 500 psig (3.4MPa). 2.0 μmol each of the above metal complex andtrisperfluorophenylborane cocatalyst as 0.005M solutions in toluene arepremixed in the drybox. After five minutes premix time, the solution istransferred to a catalyst addition tank and injected into the reactor.The polymerization conditions are maintained for 15 minutes withethylene on demand. The resulting solution is removed from the reactor,and a hindered phenol antioxidant (Irganox™ 1010 from Ciba GeigyCorporation) is added to the solution. The polymer formed is dried in avacuum oven set at 120° C. for about 20 hours.

What is claimed is:
 1. A supported catalyst for use in polymerizingaddition polymerizable monomers comprising:1) a metal complexcorresponding to the formula: ##STR4## or a dimer, solvated adduct,chelated derivative or mixture thereof, wherein: L independently eachoccurrence is a group that is bound to M via a delocalized, π-bond, saidL containing up to 50 nonhydrogen atoms; M is a metal of Group 3, 4 orthe Lanthanide series of the Periodic Table of the Elements; Z is acovalently bound, divalent substituent of up to 50 non-hydrogen atomshaving the formula, --(ER*₂)_(m) --, wherein E independently eachoccurrence is carbon, silicon or germanium, R* independently eachoccurrence is selected from the group consisting of C₁₋₂₀ hydrocarbyl,and C₁₋₂₀ hydrocarbyloxy, with the proviso that in at least oneoccurrence R* is C₁₋₂₀ hydrocarbyloxy, and m is an integer from 1 to 3;X' is a neutral Lewis base ligand having up to 20 non-hydrogen atoms; X"independently each occurrence is a monovalent, anionic moiety selectedfrom hydride, halo, hydrocarbyl, silyl, germyl, hydrocarbyloxy, amide,siloxy, halohydrocarbyl, halosilyl, silylhydrocarbyl, andaminohydrocarbyl having up to 20 non-hydrogen atoms, or two X" groupstogether form a divalent hydrocarbadiyl or neutral hydrocarbon group; nis a number from 0 to 3; and p is an integer from 0 to 2 2) anactivating cocatalyst, and 3) an aluminum or silicon containingsubstrate containing hydroxyl, --(Si--R)═, or --(Si--Cl)═ functionallywherein R is C₁₋₁₀ hydrocarbyl, with the proviso that the surfacehydroxyl content of a hydroxyl functionalized substrate is less than 0.8mmol/g;or an aluminum or silicon containing substrate that has beentreated with an aluminum component selected from the group consisting ofalumoxane and aluminum compounds of the formula AlR'_(x) R² _(y'),wherein R' independently each occurrence is hydride or R, R² is hydride,R or OR, x' is 2 or 3, y' is 0 or 1 and the sum of x' and y' is three,said complex being chemically bound to the substrate by reaction of thehydrocarbyloxy functionality thereof with aluminum or silicon atoms orhydroxyl, silane or chlorosilane functionality of the substrate.
 2. Acatalyst according to claim 1 wherein the metal complex corresponds tothe formula: ##STR5## wherein: M is titanium, zirconium or hafnium, inthe +2, +3 or +4 formal oxidation state;E independently each occurrenceis carbon or silicon; R* independently each occurrence is selected fromthe group consisting of C₁₋₆ hydrocarbyl, and C₁₋₆ hydrocarbyloxy, withthe proviso that in at least one occurrence R* is C₁₋₆ hydrocarbyloxy; mis 1 or 2; R' independently in each occurrence is selected from thegroup consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, haloand combinations thereof, said R' having up to 20 non-hydrogen atomseach, or adjacent R' groups together form a divalent derivative that isa hydrocarbadiyl, siladiyl or germadiyl group; X' is a conjugated dienehaving from 4 to 30 non-hydrogen atoms, which forms a π-complex with Mwhen M is in the +2 formal oxidation state, whereupon n is 1 and p is 0;X" each occurrence is an anionic ligand group that is covalently bondedto M when M is in the +3 or +4 formal oxidation state, whereupon n is 0and p is 1 or 2, and optionally two X" groups together form a divalentanionic ligand group.
 3. A catalyst according to claim 2 wherein R'independently in each occurrence is selected from the group consistingof hydrogen, methyl, ethyl, and all isomers of propyl, butyl, pentyl andhexyl, as well as cyclopentyl, cyclohexyl, norbornyl, benzyl, andtrimethyl silyl; or adjacent R' groups are linked together therebyforming a fused ring system,or a dimer, solvated adduct, chelatedderivative or mixture thereof.
 4. A catalyst according to claim 1,wherein X' is, η⁴ -1,4-diphenyl-1,3-butadiene; η⁴ -1,3-pentadiene; η⁴-1-phenyl-1,3-pentadiene; η⁴ -1,4-dibenzyl-1,3-butadiene; η⁴-2,4-hexadiene; η⁴ -3-methyl-1,3-pentadiene; η⁴-1,4-ditolyl-1,3-butadiene; or η⁴-1,4-bis(trimethylsilyl)-1,3-butadiene,or a dimer, solvated adduct,chelated derivative or mixture thereof.
 5. A catalyst according to claim1, wherein X" is hydride, chloride, methyl, benzyl, phenyl, tolyl,t-butyl, methoxide, or trimethylsilyl or two X" groups together are1,4-butanediyl, s-cis(1,3-butadiene), ors-cis(2,3-dimethyl-1,3-butadiene), or a dimer, solvated adduct, chelatedderivative or mixture thereof.
 6. A catalyst according to claim 1,wherein E is silicon, m is 1, and R* in at least one occurrence ismethoxide, ethoxide or isopropoxide,or a dimer, solvated adduct,chelated derivative or mixture thereof.
 7. A catalyst according to claim1 wherein L is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl,or one of the foregoing groups further substituted with one or moremethyl, ethyl, propyl, butyl, pentyl, hexyl, (including branched andcyclic isomers), norbornyl, benzyl, phenyl, or naphthyl groups, or adimer, solvated adduct, chelated derivative or mixture thereof.
 8. Aprocess for polymerizing an α-olefin, comprising contacting an α-olefinor a mixture of α-olefins with a catalyst system according to any ofclaims 1-7.